JP5170685B2 - Conductive bonding material and electronic device - Google Patents

Conductive bonding material and electronic device Download PDF

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JP5170685B2
JP5170685B2 JP2008532041A JP2008532041A JP5170685B2 JP 5170685 B2 JP5170685 B2 JP 5170685B2 JP 2008532041 A JP2008532041 A JP 2008532041A JP 2008532041 A JP2008532041 A JP 2008532041A JP 5170685 B2 JP5170685 B2 JP 5170685B2
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metal powder
powder
melting point
temperature
metal
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JPWO2008026517A1 (en
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昭博 野村
英清 高岡
公介 中野
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株式会社村田製作所
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02Electrically-conducting adhesives
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203Fillers and particles
    • H05K2201/0263Details about a collection of particles
    • H05K2201/0272Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10613Details of electrical connections of non-printed components, e.g. special leads
    • H05K2201/10621Components characterised by their electrical contacts
    • H05K2201/10636Leadless chip, e.g. chip capacitor or resistor
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/04Soldering or other types of metallurgic bonding
    • H05K2203/0425Solder powder or solder coated metal powder
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852Adhesive compositions
    • Y10T428/2857Adhesive compositions including metal or compound thereof or natural rubber
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31678Of metal

Description

本発明は導電性接合材料、及び電子装置に関し、より詳しくはチップ型電子部品やプリント配線基板等の電気構造物同士を接合する導電性接合材料、及び複数の電気構造物が前記導電性接合材料を介して接合された電子装置に関する。   The present invention relates to a conductive bonding material and an electronic device, and more specifically, a conductive bonding material for bonding electric structures such as a chip-type electronic component and a printed wiring board, and a plurality of electric structures including the conductive bonding material. The present invention relates to an electronic device joined via
従来より、熱硬化性樹脂と金属粉末とを含有した導電性接着剤を使用し、複数の電気構造物同士を接合した電子装置が知られている。   2. Description of the Related Art Conventionally, there has been known an electronic device in which a plurality of electrical structures are joined together using a conductive adhesive containing a thermosetting resin and metal powder.
例えば、特許文献1には、図6に示すように、基板101に第1の電極102が形成されると共に、電子デバイス103に第2の電極104が形成され、第1の電極102及び第2の電極104は金属微粒子の融着により導通が確保された電極接続部105に接続されると共に、電極接続部105間には導電性接着剤からなる中間接続部106が介在され、かつ前記金属微粒子は、前記導電性接着剤の熱硬化温度以下で融着し、前記導電性接着剤は、該導電性接着剤の熱硬化温度以下では融着しない粒径の導電性フィラーを含有した接続構造体が提案されている。   For example, in Patent Document 1, as shown in FIG. 6, the first electrode 102 is formed on the substrate 101, the second electrode 104 is formed on the electronic device 103, and the first electrode 102 and the second electrode 102 are formed. The electrode 104 is connected to an electrode connecting portion 105 in which conduction is ensured by fusion of metal fine particles, an intermediate connecting portion 106 made of a conductive adhesive is interposed between the electrode connecting portions 105, and the metal fine particles Is bonded at a temperature equal to or lower than the heat curing temperature of the conductive adhesive, and the conductive adhesive contains a conductive filler having a particle size that does not melt below the heat curing temperature of the conductive adhesive. Has been proposed.
この特許文献1では、電極接続部105が、導電性接着剤の熱硬化温度以下で融着が起こるAg等の金属微粒子と、導電性接着剤の熱硬化温度以下では融着が起こらない粒径の導電性フィラーと、接着剤とからなる導電性接着剤で構成されている。   In Patent Document 1, the electrode connecting portion 105 has a metal particle such as Ag that causes fusion at a temperature lower than the heat curing temperature of the conductive adhesive, and a particle size at which the fusion does not occur at a temperature lower than the heat curing temperature of the conductive adhesive. It is comprised with the conductive adhesive which consists of these conductive fillers, and an adhesive agent.
そして、特許文献1では、加熱硬化処理により電極接続部105に含有される金属微粒子を介して第1及び第2の電極102、104と導電性フィラーとを融着させ、さらに前記金属微粒子を介して導電性フィラー同士を融着させ、これにより界面での接着力を向上させている。   And in patent document 1, the 1st and 2nd electrodes 102 and 104 and a conductive filler are fuse | melted through the metal microparticles contained in the electrode connection part 105 by heat-hardening process, and also via the said metal microparticles. Thus, the conductive fillers are fused together, thereby improving the adhesion at the interface.
また、特許文献2には、図7に示すように、第1の基板107と第2の基板108とが熱伝導性材料109で接合された熱伝導性接合体が提案されている。   Patent Document 2 proposes a thermally conductive joined body in which a first substrate 107 and a second substrate 108 are joined with a thermally conductive material 109 as shown in FIG.
特許文献2の熱伝導性材料109は、有機酸を含有した熱硬化性樹脂110と熱伝導性フィラーとを含み、前記熱伝導性フィラーが熱硬化性樹脂110の熱硬化温度より高い融点を有する第1のフィラー111と、熱硬化性樹脂110の熱硬化温度より低い融点を有する第2のフィラー112とからなる熱伝導性材料が提案されている。   The thermally conductive material 109 of Patent Document 2 includes a thermosetting resin 110 containing an organic acid and a thermally conductive filler, and the thermally conductive filler has a melting point higher than the thermosetting temperature of the thermosetting resin 110. A thermally conductive material composed of a first filler 111 and a second filler 112 having a melting point lower than the thermosetting temperature of the thermosetting resin 110 has been proposed.
また、特許文献2では、熱硬化性樹脂110及び熱伝導性フィラー111、112の総量に対する熱伝導性フィラー(第1及び第2のフィラー)の体積比率が、50体積%(89重量%に相当)となるように調製された実施例が開示されている。   Moreover, in patent document 2, the volume ratio of the heat conductive filler (1st and 2nd filler) with respect to the total amount of the thermosetting resin 110 and the heat conductive filler 111,112 is 50 volume% (equivalent to 89 weight%). ) Are prepared.
特許文献2では、熱伝導性フィラーが、熱硬化性樹脂110の熱硬化温度より低い融点を有する第2のフィラー112を含むことから、熱硬化性樹脂110が硬化する前に第2のフィラー112が溶融し、第1のフィラー111と第2のフィラー112とが融着する。また、熱伝導性フィラーが、熱硬化性樹脂の熱硬化温度より高い融点を有する第1のフィラー111を含むことから、熱硬化性樹脂110の硬化後も第1のフィラー111がその形態を維持し、これにより熱抵抗の増加を抑制できる。しかも、熱伝導性材料が、熱硬化性樹脂110と熱伝導性フィラーとを含むため、接合温度を低くでき、かつ樹脂系材料をベースとするために弾性率が低くなり、熱応力の低減が可能となる。そしてこれにより、高い熱伝導性を有し、接続信頼性をも良好な熱伝導性材料を得ようとしている。   In Patent Document 2, since the thermally conductive filler includes the second filler 112 having a melting point lower than the thermosetting temperature of the thermosetting resin 110, the second filler 112 is cured before the thermosetting resin 110 is cured. Melts, and the first filler 111 and the second filler 112 are fused. In addition, since the thermally conductive filler includes the first filler 111 having a melting point higher than the thermosetting temperature of the thermosetting resin, the first filler 111 maintains its form even after the thermosetting resin 110 is cured. Thus, an increase in thermal resistance can be suppressed. In addition, since the heat conductive material includes the thermosetting resin 110 and the heat conductive filler, the bonding temperature can be lowered, and since the resin-based material is used as a base, the elastic modulus is lowered and the thermal stress is reduced. It becomes possible. As a result, a heat conductive material having high thermal conductivity and good connection reliability is being obtained.
特開2005−93826号公報(請求項1、請求項6)Japanese Patent Laying-Open No. 2005-93826 (Claims 1 and 6) 特開2004−335872号公報(請求項1、段落番号〔0040〕等)。JP 2004-335872 A (Claim 1, paragraph number [0040], etc.).
しかしながら、特許文献1では、電極接続部105は、導電性接着剤の熱硬化温度以下で溶融する金属微粒子が融着されて導通性が確保されるものの、中間接続部106は、導電性フィラー同士の接触のみで導通性が確保されているため、該中間接続部106においては導通性が劣るという問題があった。   However, in Patent Document 1, although the electrode connection portion 105 is fused with metal fine particles that melt below the heat curing temperature of the conductive adhesive to ensure conductivity, the intermediate connection portion 106 is made of conductive fillers. Since the continuity is ensured only by the contact, the intermediate connection portion 106 has a problem of poor continuity.
この問題を回避するために、導電性接着剤の熱硬化温度で溶融する低融点の金属粉末を導電性接着剤に含有させる方法が考えられる。   In order to avoid this problem, a method is conceivable in which the conductive adhesive contains a low melting point metal powder that melts at the heat curing temperature of the conductive adhesive.
ところが、複数の電気構造物同士が接合された接合構造体をマザーボードなどに実装する場合、リフロー加熱処理が繰り返し行われたり急激な温度変化を伴う熱衝撃が負荷され、接続構造体が長時間高温雰囲気下に晒されるおそれがある。このため前記低融点金属粉末が再溶融してしまい、十分な固着強度を得ることができないという問題が生じる。しかも、この場合、熱衝撃等によって溶融と硬化とが繰り返されると、電極接続部105と中間接続部106との接合界面が剥離するおそれがある。   However, when a bonding structure in which a plurality of electrical structures are bonded to each other is mounted on a motherboard or the like, the reflow heat treatment is repeatedly performed or a thermal shock with a sudden temperature change is applied, and the connection structure is heated for a long time. There is a risk of exposure to the atmosphere. For this reason, the said low melting metal powder will remelt and the problem that sufficient fixing strength cannot be obtained arises. In addition, in this case, if melting and curing are repeated due to thermal shock or the like, the bonding interface between the electrode connecting portion 105 and the intermediate connecting portion 106 may be peeled off.
特に、リフロー加熱処理では、環境面への配慮等からPbフリーはんだを使用することが一般的となってきているが、このPbフリーはんだは溶融温度が270℃〜280℃と高温であり、したがって硬化した金属が再溶融し、接合界面での剥離がより起こり易くなる。   In particular, in reflow heat treatment, it has become common to use Pb-free solder due to environmental considerations, etc., but this Pb-free solder has a melting temperature as high as 270 ° C. to 280 ° C. The hardened metal is remelted and peeling at the bonding interface is more likely to occur.
また、特許文献2では、熱伝導性フィラーの含有量や、第1のフィラー及び第2のフィラーの粒径については何ら考慮されていない。すなわち、これら熱伝導性フィラーの含有量や、第1のフィラー及び第2のフィラーの粒径によっては、加熱硬化後の接合面に対する固着強度が低下するおそれがあり、また高温多湿下に長時間晒されると接続抵抗が高くなって導電性の低下を招くおそれがある。   Moreover, in patent document 2, nothing is considered about content of a heat conductive filler, and the particle size of a 1st filler and a 2nd filler. That is, depending on the content of these heat conductive fillers and the particle diameters of the first filler and the second filler, there is a risk that the adhesion strength to the joint surface after heat curing may be reduced, and it is long for a long time under high temperature and high humidity. If exposed, the connection resistance may increase and the conductivity may decrease.
本発明はこのような事情に鑑みなされたものであって、リフロー加熱処理が繰り返さたり急激な温度変化を伴う熱衝撃が負荷された場合であっても、良好な導通性と高い接続強度を有する導電性接合材料及びこれを用いた電子装置を提供することを目的とする。   The present invention has been made in view of such circumstances, and has good conductivity and high connection strength even when the reflow heat treatment is repeated or a thermal shock with a sudden temperature change is applied. It is an object of the present invention to provide a conductive bonding material and an electronic device using the same.
上記目的を達成するために本発明に係る導電性接合材料は、熱硬化性樹脂と、該熱硬化性樹脂の熱硬化温度以下の温度で溶融するSn−Bi合金粉末からなる第1の金属粉末と、前記熱硬化性樹脂の熱硬化温度以下の温度で溶融せず、かつ前記熱硬化性樹脂の加熱硬化時に前記第1の金属粉末と反応して300℃以上の高融点を有する反応物を生成する第2の金属粉末と、該第2の金属粉末の表面に形成される酸化物を除去する還元性物質とを含有し、前記第1の金属粉末及び前記第2の金属粉末の含有量が、総計で75〜88重量%であり、かつ、前記第1の金属粉末の平均粒径D1と前記第2の金属粉末の平均粒径D2との粒径比D1/D2が、0.5〜6.0であることを特徴としている。 In order to achieve the above object, the conductive bonding material according to the present invention is a first metal powder comprising a thermosetting resin and an Sn-Bi alloy powder that melts at a temperature not higher than the thermosetting temperature of the thermosetting resin. And a reaction product that does not melt at a temperature lower than or equal to the thermosetting temperature of the thermosetting resin and that has a high melting point of 300 ° C. or more by reacting with the first metal powder during the heat curing of the thermosetting resin. A content of the first metal powder and the second metal powder, including a second metal powder to be generated and a reducing substance that removes an oxide formed on the surface of the second metal powder. Is 75 to 88% by weight in total, and the particle diameter ratio D1 / D2 between the average particle diameter D1 of the first metal powder and the average particle diameter D2 of the second metal powder is 0.5 It is characterized by being -6.0.
また、本発明の導電性接合材料は、前記第1の金属粉末及び前記第2の金属粉末の総量に対する前記第1の金属粉末の体積比率は、25〜75体積%であることを特徴としている。   The conductive bonding material of the present invention is characterized in that the volume ratio of the first metal powder to the total amount of the first metal powder and the second metal powder is 25 to 75% by volume. .
また、本発明の導電性接合材料は、前記第2の金属粉末は、前記第2の金属粉末よりも前記第1の金属粉末に対して濡れ性が高く、かつ、前記熱硬化性樹脂の熱硬化温度以下の温度で溶融する低融点金属で被覆されていることを特徴とし、また、前記低融点金属は、Snを含有した金属であることを特徴としている。   In the conductive bonding material of the present invention, the second metal powder has higher wettability with respect to the first metal powder than the second metal powder, and the heat of the thermosetting resin. It is characterized by being coated with a low melting point metal that melts at a temperature lower than the curing temperature, and the low melting point metal is a metal containing Sn.
さらに、本発明の導電性接合材料は、前記第2の金属粉末は、該第2の金属粉末よりも前記第1の金属粉末に対して濡れ性の高い金属で被覆されていることを特徴とするのも好ましく、また、前記濡れ性が高い金属は、貴金属であることを特徴とするのも好ましい。   Furthermore, the conductive bonding material of the present invention is characterized in that the second metal powder is coated with a metal having higher wettability with respect to the first metal powder than the second metal powder. It is also preferable that the metal having high wettability is a noble metal.
また、本発明に係る電子装置は、第1の電極を有する第1の電気構造物と、第2の電極を有する第2の電気構造物とを備えた電子装置であって、前記第1の電極と前記第2の電極とが、上述した導電性接合材料を介して電気的に接続されると共に、前記第1の金属粉末と前記第2の金属粉末との界面、前記第1の金属粉末と前記第1の電極との界面、及び前記第1の金属粉末と前記第2の電極との界面のうちの少なくとも1つの界面は、300℃以上の高融点を有する反応物で結合されていることを特徴としている。   An electronic device according to the present invention is an electronic device including a first electric structure having a first electrode and a second electric structure having a second electrode, wherein the first electric structure has the first electrode. The electrode and the second electrode are electrically connected via the above-described conductive bonding material, and the interface between the first metal powder and the second metal powder, the first metal powder And the first electrode, and at least one of the first metal powder and the second electrode is bonded with a reactant having a high melting point of 300 ° C. or higher. It is characterized by that.
本発明の導電性接合材料によれば、熱硬化性樹脂と、該熱硬化性樹脂の熱硬化温度以下の温度で溶融するSn−Bi合金粉末からなる第1の金属粉末と、前記熱硬化性樹脂の熱硬化温度以下の温度で溶融せず、かつ前記熱硬化性樹脂の加熱硬化時に前記第1の金属粉末と反応して300℃以上の高融点を有する反応物を生成する第2の金属粉末(例えば、Cu粉末)と、該第2の金属粉末の表面に形成される酸化物を除去する還元性物質とを含有し、前記第1の金属粉末及び前記第2の金属粉末の含有量が、総計で75〜88重量%であり、かつ、前記第1の金属粉末の平均粒径D1と前記第2の金属粉末の平均粒径D2との粒径比D1/D2が、0.5〜6.0であるので、加熱硬化時には第1の金属粉末であるSn−Bi合金粉末が濡れ拡がって第2の金属粉末と電気的に接続され、導電パスが形成される。そして、第1の金属粉末は第2の金属粉末と反応して300℃では溶融しない高融点反応物を生成することから、導通性に優れ、かつ強固な固着力を有する接続信頼性の優れた導電性接合材料を得ることができる。 According to the conductive bonding material of the present invention, a thermosetting resin, a first metal Powder consisting of Sn-Bi alloy powder melting by heat curing temperature below the temperature of the thermosetting resin, the thermosetting A second product that does not melt at a temperature lower than the thermosetting temperature of the curable resin and reacts with the first metal powder during the heat curing of the thermosetting resin to produce a reactant having a high melting point of 300 ° C. or higher. Containing a metal powder (for example, Cu powder) and a reducing substance that removes oxides formed on the surface of the second metal powder, and containing the first metal powder and the second metal powder The total amount is 75 to 88% by weight, and the particle size ratio D1 / D2 between the average particle size D1 of the first metal powder and the average particle size D2 of the second metal powder is 0.00. since it is from 5 to 6.0, at the time of heat curing wet Sn-Bi alloy powder, which is a first metal powder The second metal powder and electrically connected Therefore, the conductive path is formed. Then, the first metal powder from generating a high-melting-point reaction product which does not melt in the reaction to 300 ° C. and the second metal powder, excellent in conductivity, and excellent connection reliability with a strong adhesive force A conductive bonding material can be obtained.
しかも、第1の金属粉末が、溶融時の体積膨張が小さいBiを含有したSn−Bi合金粉末で形成されているので、たとえ第1の金属粉末の第2の金属粉末への濡れ拡がりが不足し、高融点反応物が十分に生成されない場合であっても、溶融時の体積膨張に伴う接合界面の破損が生じ難く、良好な固着強度を確保することができる。 And since the 1st metal powder is formed with the Sn-Bi alloy powder containing Bi with the small volume expansion at the time of a fusion | melting , even if the 1st metal powder spreads to the 2nd metal powder, the first metal powder is insufficient. Even when the high melting point reactant is not sufficiently produced, the bonding interface is hardly damaged due to the volume expansion at the time of melting, and good fixing strength can be ensured.
また、前記第1の金属粉末及び前記第2の金属粉末の総量に対する前記第1の金属粉末の体積比率は、25〜75体積%であるので、第1の金属粉末の占める体積比率が適正範囲に維持され、多数の導電パスを容易に形成することができる。すなわち、第1の金属粉末が不足したり、或いは第2の金属粉末と反応しなかった未反応の第1の金属粉末が残留するのが抑制され、所望の導通性と接続信頼性を確保することができる導電性接合材料を得ることができる。   Further, the volume ratio of the first metal powder to the total amount of the first metal powder and the second metal powder is 25 to 75% by volume, so that the volume ratio occupied by the first metal powder is in an appropriate range. Thus, a large number of conductive paths can be easily formed. That is, the shortage of the first metal powder or the remaining of the unreacted first metal powder that has not reacted with the second metal powder is suppressed, and desired continuity and connection reliability are ensured. A conductive bonding material that can be obtained can be obtained.
また、前記第2の金属粉末は、前記第2の金属粉末よりも前記第1の金属粉末に対して濡れ性が高く、かつ、前記熱硬化性樹脂の熱硬化温度以下の温度で溶融する低融点金属(例えば、Sn)で被覆されているので、熱硬化性樹脂の加熱硬化時には第1の金属粉末が第2の金属粉末の表面に濡れ拡がりやすくなる。そしてその結果、融点が300℃以上の高融点反応物の生成を促進させることができ、より良好な導通性を有する導電パスを形成することができ、また接合界面の固着強度をより一層向上させることができる。   Further, the second metal powder has higher wettability with respect to the first metal powder than the second metal powder and melts at a temperature lower than the thermosetting temperature of the thermosetting resin. Since it is covered with a melting point metal (for example, Sn), the first metal powder tends to wet and spread on the surface of the second metal powder when the thermosetting resin is heat-cured. As a result, the generation of a high melting point reactant having a melting point of 300 ° C. or higher can be promoted, a conductive path having better conductivity can be formed, and the bonding strength of the bonding interface can be further improved. be able to.
さらに、前記第2の金属粉末は、該第2の金属粉末よりも前記第1の金属粉末に対して濡れ性の高い金属(例えば、Au等の貴金属)で被覆された場合も、上述と同様の作用効果を奏することができる。   Further, when the second metal powder is coated with a metal (for example, a noble metal such as Au) having higher wettability with respect to the first metal powder than the second metal powder, the same as described above. The effect of this can be achieved.
また、本発明の電子装置によれば、上述した導電性接合材料を介して第1の電気構造物の第1の電極と第2の電気構造物の第2の電極とが電気的に接続されると共に、前記第1の金属粉末と前記第2の金属粉末との界面、前記第1の金属粉末と前記第1の電極との界面、及び前記第1の金属粉末と前記第2の電極との界面のうちの少なくとも1つの界面は、300℃以上の高融点を有する高融点反応物で結合されているので、良好な導通性を有する導電パスが形成され、これらの接合界面は高融点反応物で固着される。   According to the electronic device of the present invention, the first electrode of the first electric structure and the second electrode of the second electric structure are electrically connected via the conductive bonding material described above. And the interface between the first metal powder and the second metal powder, the interface between the first metal powder and the first electrode, and the first metal powder and the second electrode. At least one of the interfaces is bonded with a high melting point reactant having a high melting point of 300 ° C. or higher, so that a conductive path having good conductivity is formed. It is fixed with objects.
したがって、第1の電気構造物と第2の電気構造物が接合された後に、リフロー加熱処理や熱衝撃が負荷され、高温雰囲気に長時間晒された場合であっても、金属の再溶融が生じるのを回避することができ、接合界面が剥離することもなく、良好な導通性と強固な界面固着力を有する機械的強度の優れた電子装置を得ることができる。   Therefore, after the first electric structure and the second electric structure are joined, reflow heat treatment or thermal shock is applied, and even if the metal is remelted even when exposed to a high temperature atmosphere for a long time. This can be avoided, and the bonding interface does not peel off, and an electronic device with excellent mechanical strength having good electrical conductivity and strong interface adhesion can be obtained.
本発明に係る導電性接合材料を使用して製造された電子装置の一実施の形態を示す概略断面図である。It is a schematic sectional drawing which shows one Embodiment of the electronic device manufactured using the electroconductive joining material which concerns on this invention. 図1の加熱硬化前におけるA部拡大図である。It is the A section enlarged view before the heat-curing of FIG. 図1の加熱硬化後におけるA部拡大図である。It is the A section enlarged view after the heat-curing of FIG. 低融点金属の平均粒径が高融点金属の平均粒径に対して過度に小さい場合の導電性接合材料の硬化状態を模式的に示す断面図である。It is sectional drawing which shows typically the hardening state of an electroconductive joining material in case the average particle diameter of a low melting metal is too small with respect to the average particle diameter of a high melting metal. 低融点金属の平均粒径が高融点金属の平均粒径に対して過度に大きい場合の導電性接合材料の硬化状態を模式的に示す断面図である。It is sectional drawing which shows typically the hardening state of an electroconductive joining material in case the average particle diameter of a low melting metal is excessively large with respect to the average particle diameter of a high melting metal. 特許文献1に記載された接続構造体の模式図である。It is a schematic diagram of the connection structure described in Patent Document 1. 特許文献2に記載された熱伝導性接合体の硬化前の状態を示す模式図である。It is a schematic diagram which shows the state before hardening of the heat conductive joining body described in patent document 2. FIG.
符号の説明Explanation of symbols
1a、1b ランド電極(第1の電極)
2 基板(第1の電気構造体)
3 チップ型電子部品(第2の電気構造体)
5a、5b 外部電極(第2の電極)
6a、6b 導電性接合材料
7 熱硬化性樹脂
8 低融点金属粉末(第1の金属粉末)
9 高融点金属粉末(第2の金属粉末)
1a, 1b Land electrode (first electrode)
2 Substrate (first electrical structure)
3 Chip-type electronic components (second electrical structure)
5a, 5b External electrode (second electrode)
6a, 6b Conductive bonding material 7 Thermosetting resin 8 Low melting point metal powder (first metal powder)
9 High melting point metal powder (second metal powder)
次に、本発明の実施の形態を詳述する。   Next, an embodiment of the present invention will be described in detail.
図1は本発明の導電性接合材料を使用して製造される電子装置の一実施の形態を模式的に示した断面図である。   FIG. 1 is a cross-sectional view schematically showing one embodiment of an electronic device manufactured using the conductive bonding material of the present invention.
すなわち、本電子装置は、ランド電極(第1の電極)1a、1bが形成されたプリント配線基板等の基板(第1の電気構造物)2上にセラミックコンデンサ等のチップ型電子部品(第2の電気構造物)3が搭載されている。   In other words, this electronic apparatus has a chip-type electronic component (second capacitor) such as a ceramic capacitor on a substrate (first electric structure) 2 such as a printed wiring board on which land electrodes (first electrodes) 1a and 1b are formed. The electrical structure 3) is mounted.
このチップ型電子部品3は、セラミック材料を主成分とする電子部品本体4の両端に外部電極(第2の電極)5a、5bが形成されており、該外部電極5a、5bとランド電極1a、1bとが導電性接合材料6a、6bで電気的に接続されている。   In this chip-type electronic component 3, external electrodes (second electrodes) 5a and 5b are formed at both ends of an electronic component main body 4 mainly composed of a ceramic material. The external electrodes 5a and 5b and the land electrodes 1a, 1b is electrically connected with conductive bonding materials 6a and 6b.
図2は、図1の加熱硬化前におけるA部拡大図である。   FIG. 2 is an enlarged view of a portion A before heat curing in FIG.
導電性接合材料6aは、熱硬化温度が例えば200℃程度の熱硬化性樹脂7と、該熱硬化性樹脂7の熱硬化温度以下の温度で溶融する低融点金属粉末(第1の金属粉末)8と、前記熱硬化性樹脂7の熱硬化温度以下の温度で溶融せず、かつ前記熱硬化性樹脂7の加熱硬化時に前記低融点金属粉末8と反応して融点が300℃以上の高融点反応物を生成する高融点金属粉末(第2の金属粉末)9と、該高融点金属粉末9の表面に形成される酸化物を除去する還元性物質(不図示)とを含有している。   The conductive bonding material 6a includes a thermosetting resin 7 having a thermosetting temperature of, for example, about 200 ° C., and a low melting point metal powder (first metal powder) that melts at a temperature not higher than the thermosetting temperature of the thermosetting resin 7. 8 and a high melting point that does not melt at a temperature lower than the thermosetting temperature of the thermosetting resin 7 and reacts with the low melting metal powder 8 during the heat curing of the thermosetting resin 7 and has a melting point of 300 ° C. or higher. It contains a refractory metal powder (second metal powder) 9 that generates a reaction product, and a reducing substance (not shown) that removes oxides formed on the surface of the refractory metal powder 9.
すなわち、この導電性接合材料6aは、熱硬化性樹脂7中に低融点金属粉末8、高融点金属粉末9、及び還元性物質(不図示)が分散されている。   That is, in the conductive bonding material 6 a, the low melting point metal powder 8, the high melting point metal powder 9, and a reducing substance (not shown) are dispersed in the thermosetting resin 7.
尚、上記反応物は、上述したように低融点金属粉末と高融点金属粉末とが反応して生成する融点が300℃以上の高融点反応物をいうが、具体的には金属間化合物又は固溶体を意味する。   The above-mentioned reactant is a high-melting-point reactant having a melting point of 300 ° C. or more generated by reacting a low-melting-point metal powder and a high-melting-point metal powder as described above. Specifically, an intermetallic compound or a solid solution is used. Means.
図3は、図1の加熱硬化後におけるA部拡大図である。   FIG. 3 is an enlarged view of part A after the heat curing of FIG.
導電性接合材料6aを外部電極5a及びランド電極1aに塗布し、熱硬化温度以上の温度で加熱処理すると、低融点金属粉末8が溶融して濡れ拡がる。そして、高融点金属粉末9、9間が低融点金属粉末8を介して接続され、多数の導電パス11が生成される。   When the conductive bonding material 6a is applied to the external electrode 5a and the land electrode 1a and heat-treated at a temperature equal to or higher than the thermosetting temperature, the low melting point metal powder 8 is melted and spreads. Then, the high melting point metal powders 9 and 9 are connected via the low melting point metal powder 8 to generate a large number of conductive paths 11.
すなわち、上記高融点金属粉末9は熱硬化性樹脂7の熱硬化温度では溶融しないため、高融点金属粉末9のみを熱硬化性樹脂7中に分散させても、導電パス11を生成するのは困難である。   That is, since the refractory metal powder 9 does not melt at the thermosetting temperature of the thermosetting resin 7, the conductive path 11 is generated even if only the refractory metal powder 9 is dispersed in the thermosetting resin 7. Have difficulty.
そこで、本実施の形態では、熱硬化性樹脂7中に該熱硬化樹脂7の熱硬化温度以下の温度で溶融する低融点金属粉末8を分散させ、加熱硬化時に熱硬化温度以上の温度で加熱することにより、低融点金属粉末8を溶融させて濡れ拡がらしている。そしてこれにより、高融点金属粉末9、9間が低融点金属粉末8で接続され、良好な導電性を有する多数の導電パス11が生成される。   Therefore, in the present embodiment, the low melting point metal powder 8 that melts at a temperature not higher than the thermosetting temperature of the thermosetting resin 7 is dispersed in the thermosetting resin 7 and heated at a temperature not lower than the thermosetting temperature at the time of heat curing. By doing so, the low melting point metal powder 8 is melted and spreads. As a result, the high melting point metal powders 9 and 9 are connected by the low melting point metal powder 8, and a large number of conductive paths 11 having good conductivity are generated.
この低融点金属粉末8は高融点金属粉末9と反応して融点が300℃以上の高融点反応物を生成することから、Pbフリーはんだを使用してリフロー加熱処理を行ったり熱衝撃などが繰り返し負荷される等、高温多湿下で長時間晒された場合であっても、接合界面の金属が再溶融することはなく、良好な固着強度を有する電子装置を得ることができる。   Since this low melting point metal powder 8 reacts with the high melting point metal powder 9 to produce a high melting point reaction product having a melting point of 300 ° C. or higher, reflow heat treatment using Pb-free solder or thermal shock is repeated. Even when it is exposed to a high temperature and high humidity for a long time, such as when it is loaded, the metal at the bonding interface is not remelted, and an electronic device having good adhesion strength can be obtained.
また、溶融した低融点金属粉末はランド電極1a、1bや外部電極5a、5bにも濡れ拡がることから、これらランド電極1a、1bや外部電極5a、5bに含まれるAg−PdやSn等の金属との間でも高融点反応物が生成され、導電パス11が形成される。したがって、これによってもランド電極1a、1b及び外部電極5a、5bと間の固着力がより強固で機械的強度の優れた電子装置を得ることができる。   Further, since the molten low melting point metal powder wets and spreads over the land electrodes 1a and 1b and the external electrodes 5a and 5b, a metal such as Ag-Pd or Sn contained in the land electrodes 1a and 1b or the external electrodes 5a and 5b. A high melting point reaction product is also generated between the two and the conductive path 11 is formed. Therefore, it is possible to obtain an electronic device with a stronger fixing force between the land electrodes 1a and 1b and the external electrodes 5a and 5b and having an excellent mechanical strength.
また、本導電性接合材料には、還元性物質が含有されており、これにより高融点金属粉末9の表面に生成される酸化物を除去することができる。すなわち、表面に生成している酸化物を除去することにより、熱硬化性樹脂7の加熱硬化時には低融点金属粉末8が高融点金属粉末9の表面に濡れ拡がりやすくなり、より導通性の高い導電パス11が形成されると共に、高融点反応物の生成を促進することができる。したがって、これによってもランド電極1a、1b及び外部電極5a、5bとの間がより一層強固な固着力を有する電子装置を得ることができる。   In addition, the conductive bonding material contains a reducing substance, whereby the oxide generated on the surface of the refractory metal powder 9 can be removed. That is, by removing the oxide generated on the surface, the low melting point metal powder 8 tends to wet and spread on the surface of the high melting point metal powder 9 when the thermosetting resin 7 is heated and cured, and the conductivity is higher. The formation of the high melting point reactant can be promoted while the pass 11 is formed. Therefore, it is possible to obtain an electronic device having an even stronger fixing force between the land electrodes 1a and 1b and the external electrodes 5a and 5b.
そして、このような還元性物質としては、還元性を有する物質、例えば、こはく酸、酢酸などの有機酸、塩酸、臭酸等を好んで使用することができるが、還元性を有するのであれば、酸以外の物質も使用することができる。   As such a reducing substance, a reducing substance, for example, organic acids such as succinic acid and acetic acid, hydrochloric acid, odorous acid and the like can be preferably used. Substances other than acids can also be used.
このように本実施の形態によれば、良好な導通性を確保しつつ、ランド電極1a、1b及び外部電極5a、5bとの接合界面が強固な固着力でもって接合された電子装置を得ることができる。   As described above, according to the present embodiment, it is possible to obtain an electronic device in which the bonding interface between the land electrodes 1a and 1b and the external electrodes 5a and 5b is bonded with a strong fixing force while ensuring good electrical conductivity. Can do.
さらに、本実施の形態では、導電性接合材料6a、6b中の低融点金属粉末8及び高融点金属粉末9の含有量、すなわち金属粉末の総含有量が、75〜88重量%に設定されている。   Furthermore, in the present embodiment, the contents of the low melting point metal powder 8 and the high melting point metal powder 9 in the conductive bonding materials 6a and 6b, that is, the total content of the metal powder is set to 75 to 88% by weight. Yes.
すなわち、導電性接合材料6a、6b中の金属粉末の総含有量が、75重量%未満に低下すると、導電性接合材料6a、6b中の金属粉末が過少であるため、加熱硬化時に低融点金属粉末8が濡れ拡がっても高融点金属粉末9と接続されず、導電パス11を生成するのが困難となり、融点が300℃以上の高融点反応物を十分に生成することができなくなる。そしてその結果、導通性の低下を招き、特に高温多湿下で長時間放置された場合は導通性低下を助長する。   That is, when the total content of the metal powder in the conductive bonding materials 6a and 6b is reduced to less than 75% by weight, the metal powder in the conductive bonding materials 6a and 6b is too small. Even if the powder 8 wets and spreads, it is not connected to the refractory metal powder 9, making it difficult to produce the conductive path 11, and it becomes impossible to sufficiently produce a refractory reactant having a melting point of 300 ° C. or higher. As a result, the conductivity is lowered, and particularly when left for a long time under high temperature and high humidity, the conductivity is reduced.
一方、導電性接合材料6a、6b中の金属粉末の総含有量が、88重量%を超えると、導電性接合材料6a、6b中の熱硬化樹脂7の含有量が過少となるため、ランド電極1a、1bや外部電極5a、5bとの間の固着強度が低下するおそれがある。   On the other hand, if the total content of the metal powder in the conductive bonding materials 6a and 6b exceeds 88% by weight, the content of the thermosetting resin 7 in the conductive bonding materials 6a and 6b becomes too small. There is a possibility that the fixing strength between 1a and 1b and the external electrodes 5a and 5b may be lowered.
そこで、本実施の形態では、導電性接合材料6a、6b中の金属粉末の総含有量は、75〜88重量%に設定されている。   Therefore, in the present embodiment, the total content of the metal powder in the conductive bonding materials 6a and 6b is set to 75 to 88% by weight.
また、低融点金属粉末8の平均粒径D1と高融点金属粉末9の平均粒径D2との粒径比D1/D2は、0.5〜6.0に設定されている。   The particle size ratio D1 / D2 between the average particle size D1 of the low melting point metal powder 8 and the average particle size D2 of the high melting point metal powder 9 is set to 0.5 to 6.0.
すなわち、粒径比D1/D2が0.5未満の場合は、高融点金属粉末9の平均粒径D2に対する低融点金属粉末8の平均粒径D1が小さ過ぎるため、低融点金属粉末8の平均粒径D1に対し高融点金属粉末9間の間隔が広くなり、図4に示すように、加熱硬化処理を行っても低融点金属粉末8が高融点金属粉末9同士を接続することができずに導電パス11を生成することができない部分が生じる。 このため、ランド電極1a、1b及び外部電極5a、5bを高融点反応物で強固に接続できない部分が生じ、高温多湿下で長時間晒されると接続抵抗が劣化するおそれがある。   That is, when the particle size ratio D1 / D2 is less than 0.5, the average particle size D1 of the low melting point metal powder 8 relative to the average particle size D2 of the high melting point metal powder 9 is too small. The interval between the refractory metal powders 9 becomes wider with respect to the particle diameter D1, and as shown in FIG. 4, the low-melting metal powder 8 cannot connect the refractory metal powders 9 to each other even when heat-curing treatment is performed. Thus, a portion where the conductive path 11 cannot be generated is generated. For this reason, a portion where the land electrodes 1a and 1b and the external electrodes 5a and 5b cannot be firmly connected with the high melting point reactant is generated, and the connection resistance may be deteriorated when exposed for a long time under high temperature and high humidity.
一方、粒径比D1/D2が6.0を超えた場合は、高融点金属粉末9の平均粒径D2に対する低融点金属粉末8の平均粒径D1が大きすぎ、導電性接合材料中の低融点金属粉末8と高融点金属粉末9との分散状態が悪化し、図5に示すように、加熱硬化時には低融点金属粉末8同士が融着し易くなる。このため、高融点金属粉末9間を接続する導電パス11の形成が不十分となる。また、高融点反応物を十分に得ることができなくなり、ランド電極1a、1b及び外部電極6a、6bとの固着力が劣化し、またリフロ−加熱処理により低融点金属粉末8が再溶融し、導通性の低下を招くおそれがある。   On the other hand, when the particle size ratio D1 / D2 exceeds 6.0, the average particle size D1 of the low melting point metal powder 8 relative to the average particle size D2 of the high melting point metal powder 9 is too large, and the low in the conductive bonding material. The dispersion state of the melting point metal powder 8 and the high melting point metal powder 9 is deteriorated, and as shown in FIG. For this reason, the formation of the conductive path 11 connecting the refractory metal powders 9 becomes insufficient. Further, the high melting point reactant cannot be sufficiently obtained, the fixing force between the land electrodes 1a and 1b and the external electrodes 6a and 6b is deteriorated, and the low melting point metal powder 8 is remelted by the reflow-heating treatment. There is a risk of lowering conductivity.
そこで、本実施の形態では、低融点金属粉末8の平均粒径D1と高融点金属粉末9の平均粒径D2との粒径比D1/D2を、0.5〜6.0に設定している。   Therefore, in the present embodiment, the particle size ratio D1 / D2 between the average particle size D1 of the low melting point metal powder 8 and the average particle size D2 of the high melting point metal powder 9 is set to 0.5 to 6.0. Yes.
また、熱硬化性樹脂7としては、加熱硬化処理により良好な接着性を有し、ランド電極1a、1b及び外部電極5a、5bとの間で十分な固着強度を有するものであれば、特に限定されるものではなく、エポキシ系、フェノール系、アクリル系の熱硬化性樹脂やポリイミド系、ポリウレタン系、メラミン系や、ウレア系の熱硬化性樹脂を使用することができるが、エポキシ系の熱硬化性樹脂が特に好んで使用される。例えば、ビスフェノールF型、ビスフェノールA型、水添ビスフェノール型、フェノールノボラック型、グリシジルアミン型、ナフタレン型、シクロペンタジエン型、シクロヘキサン型、ヘキサンテトラヒドロキシフェノールエタン型、ヒダントイン型、ポリグリコール型、エーテル型のエポキシ樹脂や、これらのエポキシ樹脂をシリコーン、ゴム、ウレタン、キレートなどで変性した変性エポキシ樹脂を好んで使用することができる。特に、エポキシ系の熱硬化性樹脂の中でもビスフェノールF型エポキシ樹脂やビスフェノールA型エポキシ樹脂等の液状タイプのものは、作業性を保つための有機溶剤を必要としないことから、環境面や作業面から好ましく、また、熱硬化性樹脂を加熱硬化する際に、有機溶剤が揮発して接合界面にボイド(空隙)を形成することもなく、より好ましい。   Further, the thermosetting resin 7 is particularly limited as long as it has good adhesiveness by heat curing treatment and has sufficient fixing strength between the land electrodes 1a and 1b and the external electrodes 5a and 5b. Epoxy-based, phenol-based, and acrylic-based thermosetting resins, polyimide-based, polyurethane-based, melamine-based, and urea-based thermosetting resins can be used. An especially preferred resin is used. For example, bisphenol F type, bisphenol A type, hydrogenated bisphenol type, phenol novolac type, glycidylamine type, naphthalene type, cyclopentadiene type, cyclohexane type, hexanetetrahydroxyphenolethane type, hydantoin type, polyglycol type, ether type Epoxy resins and modified epoxy resins obtained by modifying these epoxy resins with silicone, rubber, urethane, chelate, etc. can be used preferably. Especially, epoxy type thermosetting resins such as bisphenol F type epoxy resin and bisphenol A type epoxy resin do not require an organic solvent to maintain workability. In addition, when the thermosetting resin is heat-cured, the organic solvent does not volatilize and a void (void) is not formed at the bonding interface, which is more preferable.
また、低融点金属粉末8としては、熱硬化性樹脂7の熱硬化温度で溶融せず、しかも溶融時の体積膨張が小さいBiを含有したSn−Bi合金粉末が使用される。このようなSn−Bi合金粉末を低融点金属粉末8に使用することにより、体積膨張に伴う接合界面の破損が生じ難く、優れた固着強度を得ることができる。 In addition, as the low melting point metal powder 8, Sn—Bi alloy powder containing Bi which does not melt at the thermosetting temperature of the thermosetting resin 7 and has a small volume expansion at the time of melting is used. By using such a Sn—Bi alloy powder for the low melting point metal powder 8, it is difficult to cause damage to the bonding interface due to volume expansion, and an excellent fixing strength can be obtained.
すなわち、マザーボード等に搭載される他の電子部品への影響を考慮して低温で加熱処理を行わざるを得ない場合、低融点金属粉末8の高融点金属粉末9への濡れ拡がりが不足し、高融点反応物を十分に生成できなくなるおそれがある。   That is, in the case where heat treatment must be performed at a low temperature in consideration of the influence on other electronic components mounted on the mother board or the like, wetting and spreading of the low melting point metal powder 8 to the high melting point metal powder 9 is insufficient. There is a possibility that a high melting point reactant cannot be sufficiently produced.
しかしながら、このような場合であっても溶融時の体積膨張が少ないBiを含有したSn−Bi粉末合金を低融点金属粉末8使用することにより、体積膨張に伴う接合界面の破損を生じ難くし、ランド電極1a、1bや外部電極5a、5bとの間の固着力を確保することができる。 However, the use of such even when contained volume expansion is small Bi when melted Sn-Bi powder alloy in a low-melting-point metal powder 8, and less likely to occur breakage of the bonding interface due to volume expansion The adhering force between the land electrodes 1a and 1b and the external electrodes 5a and 5b can be ensured.
また、高融点金属粉末9としては、熱硬化性樹脂7の熱硬化温度以下の温度で溶融せず、かつ熱硬化性樹脂7の加熱硬化時に低融点金属粉末8と反応して融点が300℃以上の高融点反応物を生成するものであれば特に限定されるものではなく、Ti、Cr、Au、Ag、Cu、Ni、Pt、Bi、Zn、Pd、Pb、Mo、Snやこれらの合金を使用することができるが、コスト面、導電性、腐食性、上記低融点金属粉末8との反応性を考慮すると、Cuを使用するのが好ましい。   Further, the high melting point metal powder 9 does not melt at a temperature lower than the thermosetting temperature of the thermosetting resin 7 and reacts with the low melting point metal powder 8 when the thermosetting resin 7 is heated and cured, resulting in a melting point of 300 ° C. It is not particularly limited as long as it generates the above high melting point reactant, and Ti, Cr, Au, Ag, Cu, Ni, Pt, Bi, Zn, Pd, Pb, Mo, Sn and alloys thereof However, it is preferable to use Cu in consideration of cost, conductivity, corrosivity, and reactivity with the low melting point metal powder 8.
そして、低融点金属粉末8として、Sn−Bi合金粉末を使用し、高融点金属粉末9としてCu粉末を使用した場合、加熱硬化時には低融点金属粉末8に含有されるSn成分がCu反応し、CuSnやCuSn等の金属間化合物が生成される。また、低融点金属粉末8にSn−Bi合金粉末を使用し、高融点金属粉末9としてAu粉末を使用した場合は、AuSnからなる金属間化合物が生成され、Ag粉末を使用した場合は、AgSnからなる金属間化合物が生成され、Ni粉末を使用した場合は、NiSnからなる金属間化合物が生成される。そして、これらの金属間化合物は、融点が300℃以上の高融点反応物であるので、リフロー加熱処理を繰り返したり、急激な温度変化を伴う熱衝撃などが繰り返し負荷されても、接合界面が再溶融することもなく、強固な固着力を確保することができる。 Then, as a low-melting-point metal powder 8, use the Sn-Bi alloy powder, when using Cu powder as a high-melting-point metal powder 9, at the time of heat curing Sn component contained in the low-melting-point metal powder 8 reacts with Cu And intermetallic compounds such as Cu 6 Sn 5 and Cu 3 Sn are produced. Further, when Sn-Bi alloy powder is used for the low melting point metal powder 8 and Au powder is used as the high melting point metal powder 9, an intermetallic compound composed of AuSn 4 is generated, and when Ag powder is used, An intermetallic compound composed of AgSn 3 is generated, and when Ni powder is used, an intermetallic compound composed of Ni 3 Sn is generated. Since these intermetallic compounds are high melting point reactants having a melting point of 300 ° C. or higher, even when reflow heat treatment is repeated or a thermal shock accompanied by a rapid temperature change is repeatedly applied, the bonding interface is restored. A strong fixing force can be ensured without melting.
尚、本発明は上記実施の形態に限定されるものではなく、種々の変形が可能である。   In addition, this invention is not limited to the said embodiment, A various deformation | transformation is possible.
例えば、金属粉末(低融点金属粉末8及び高融点金属粉末9)の総量に対する低融点金属粉末8の体積比率は、25〜75体積%が好ましい。   For example, the volume ratio of the low melting point metal powder 8 to the total amount of the metal powders (the low melting point metal powder 8 and the high melting point metal powder 9) is preferably 25 to 75% by volume.
これは、低融点金属粉末8の体積比率が金属粉末の総量に対し25体積%未満になると、低融点金属粉末8の占める体積比率が少なくなって導電パス11の形成が妨げられ、導通性の低下を招く傾向があり、一方で低融点金属粉末8の体積比率が金属粉末の総量に対し75体積%を超えると、高融点金属粉末9と反応しない未反応の低融点金属粉末8が残留し、導通性の低下を招いたり、高温での接続信頼性が低下傾向となるからである。   This is because when the volume ratio of the low melting point metal powder 8 is less than 25% by volume with respect to the total amount of the metal powder, the volume ratio occupied by the low melting point metal powder 8 is reduced and the formation of the conductive path 11 is hindered. On the other hand, when the volume ratio of the low melting point metal powder 8 exceeds 75% by volume with respect to the total amount of the metal powder, unreacted low melting point metal powder 8 that does not react with the high melting point metal powder 9 remains. This is because the conductivity is lowered and the connection reliability at a high temperature tends to be lowered.
また、高融点金属粉末9を、該高融点金属粉末9よりも低融点金属粉末8に対して濡れ性が高い金属で被覆するのも好ましい。このように高融点金属粉末9よりも低融点金属粉末8に対して濡れ性が高い金属で高融点金属粉末9を被覆することにより、熱硬化性樹脂7の加熱硬化時には低融点金属粉末8が高融点金属粉末9の表面に濡れ拡がりやすくなる。そしてその結果、融点が300℃以上の高融点反応物の生成を促進させることができ、より導通性の高い導電パス11を形成でき、より強固な界面固着力を得ることができる。   It is also preferable to coat the high melting point metal powder 9 with a metal having higher wettability with respect to the low melting point metal powder 8 than the high melting point metal powder 9. Thus, by coating the high melting point metal powder 9 with a metal having higher wettability with respect to the low melting point metal powder 8 than the high melting point metal powder 9, the low melting point metal powder 8 is formed when the thermosetting resin 7 is heated and cured. It becomes easy to wet and spread on the surface of the refractory metal powder 9. As a result, generation of a high melting point reactant having a melting point of 300 ° C. or higher can be promoted, a conductive path 11 having higher conductivity can be formed, and a stronger interfacial adhesion force can be obtained.
そして、このような濡れ性の高い金属としては、Sn、Sn−Biなどの熱硬化性樹脂の熱硬化温度以下で溶融する金属やAu、Ag、Pt、Pd等の貴金属を使用することができるが、コスト面や高融点反応物の強度、耐久性を考慮すると、Snを使用するのが好ましい。 And, as such wettability metal having high, Sn, metal or Au melts by the heat curing temperature of Sn-B i of which thermosetting resin or less, Ag, Pt, may be used a noble metal such as Pd However, it is preferable to use Sn in consideration of the cost and the strength and durability of the high melting point reactant.
また、濡れ性の高い金属としては、熱硬化性樹脂の熱硬化温度では溶融せずに低融点金属粉末8と反応することで熱硬化性樹脂の熱硬化温度で溶融する金属種を使用することもできる。   Further, as the metal having high wettability, a metal species that does not melt at the thermosetting temperature of the thermosetting resin but reacts with the low melting point metal powder 8 to melt at the thermosetting temperature of the thermosetting resin is used. You can also.
次に、本発明の実施例を具体的に説明する。   Next, examples of the present invention will be specifically described.
〔導電性接合材料の調製〕
熱硬化性樹脂としてビスフェノールF型液状エポキシ樹脂、反応性稀釈材としてターシャルブチルグリシジルエーテル、硬化剤としてアミン化合物、前記硬化剤の反応抑制剤としてホウ素化合物とエポキシ樹脂との混合物、還元性物質としてこはく酸を用意した。
(Preparation of conductive bonding material)
Bisphenol F type liquid epoxy resin as thermosetting resin, tertiary butyl glycidyl ether as reactive diluent, amine compound as curing agent, mixture of boron compound and epoxy resin as reaction inhibitor of the curing agent, as reducing substance Succinic acid was prepared.
また、平均粒径D1が10μmで融点が139℃のSn−58Bi粉末(比重:8.93)(低融点金属粉末)を用意し、さらに平均粒径D2が5μmで融点が約1080℃のCu粉末(比重:8.75)(高融点金属粉末)を用意した。尚、Sn−58Bi粉末の平均粒径D1とCu粉末の平均粒径D2との粒径比D1/D2は2.0である。   In addition, Sn-58Bi powder (specific gravity: 8.93) (low melting metal powder) having an average particle diameter D1 of 10 μm and a melting point of 139 ° C. is prepared, and Cu having an average particle diameter D2 of 5 μm and a melting point of about 1080 ° C. Powder (specific gravity: 8.75) (refractory metal powder) was prepared. In addition, the particle diameter ratio D1 / D2 of the average particle diameter D1 of Sn-58Bi powder and the average particle diameter D2 of Cu powder is 2.0.
次に、ビスフェノールF型液状エポキシ樹脂100重量部に対し、ターシャルブチルグリシジルエーテル及びアミン化合物をそれぞれ25重量部、ホウ素化合物とエポキシ樹脂の混合物を12.5重量部、こはく酸を15重量部秤量し、さらに、金属粉末(Sn−58Bi粉末及びCu粉末)の総含有量が70〜93重量%となり、かつ前記金属粉末の総量に対するSn−58Bi粉末の体積比率が50体積%となるように秤量し、これら秤量物を乳鉢に投入し、乳棒で約15分間撹拌して混合し、試料番号1〜6の導電性接合材料を作製した。   Next, 25 parts by weight of tertiary butyl glycidyl ether and amine compound, 12.5 parts by weight of a mixture of boron compound and epoxy resin, and 15 parts by weight of succinic acid are weighed with respect to 100 parts by weight of bisphenol F type liquid epoxy resin. Further, weighing is performed so that the total content of the metal powder (Sn-58Bi powder and Cu powder) is 70 to 93% by weight, and the volume ratio of the Sn-58Bi powder to the total amount of the metal powder is 50% by volume. Then, these weighed materials were put in a mortar, mixed with stirring for about 15 minutes with a pestle, and conductive bonding materials of sample numbers 1 to 6 were produced.
〔評価試料の作製〕
厚さ0.7mmのアルミナ基板上の所定位置にAg−Pdペーストを塗布し、焼付け処理を施し、アルミナ基板上に間隔が0.8mmの一対のランド電極を形成した。
[Production of evaluation samples]
An Ag—Pd paste was applied to a predetermined position on an alumina substrate having a thickness of 0.7 mm and baked to form a pair of land electrodes with a spacing of 0.8 mm on the alumina substrate.
次いで、厚さ50μmのメタルマスクを使用してランド電極上に上記導電性接合材料を塗布した。   Next, the conductive bonding material was applied onto the land electrode using a metal mask having a thickness of 50 μm.
次に、外部電極がSnからなる縦:1,6mm、横:0.8mm、厚さ:0.8mmのチップ型抵抗部品を前記導電性接合材料上に載置し、温度200℃の下、30分間、エアーオーブン中で加熱処理を行い、試料番号1〜6の試料を得た。   Next, a chip type resistance component having external electrodes made of Sn and having a length of 1,6 mm, a width of 0.8 mm, and a thickness of 0.8 mm is placed on the conductive bonding material, and the temperature is 200 ° C. Heat treatment was performed in an air oven for 30 minutes, and samples Nos. 1 to 6 were obtained.
〔特性評価〕
試料番号1〜6の各試料について、ミリオームハイテスタ(HIOKI社製:3224型)を使用してランド電極間の接続抵抗の初期値Rを測定し、またボンドテスタ(DAGE社製:シリーズ4000)を使用して固着強度の初期値Sを測定した。
(Characteristic evaluation)
For each of the samples Nos. 1 to 6, the initial value R 0 of the connection resistance between the land electrodes was measured using a milliohm high tester (manufactured by HIOKI: model 3224), and a bond tester (manufactured by DAGE: series 4000). Was used to measure the initial value S 0 of the fixing strength.
次いで、温度105℃、湿度100%の高温多湿下、48時間PCT(プレッシャークッカーテスト)を行い、PCT後の抵抗値R及び固着強度Sを測定し、さらに、下記数式(1)に基づいてPCT後の抵抗変化率ΔRを算出した。Subsequently, a PCT (pressure cooker test) is performed for 48 hours under a high temperature and high humidity of a temperature of 105 ° C. and a humidity of 100%, a resistance value R 1 and a fixing strength S 1 after PCT are measured, and further, based on the following formula (1) The resistance change rate ΔR 1 after PCT was calculated.
ΔR=(R−R)/R×100…(1)
さらに、試料番号1〜6の各試料について、最高温度が270℃に調整されたリフロー炉に5回通過させてリフロー加熱処理を行った。そして、リフロー加熱処理後の抵抗値R及び固着強度Sを測定し、リフロー後の抵抗変化率ΔRを数式(2)に基づいて算出した。
ΔR 1 = (R 1 −R 0 ) / R 0 × 100 (1)
Further, each of the samples Nos. 1 to 6 was subjected to reflow heat treatment by passing the sample 5 times through a reflow furnace whose maximum temperature was adjusted to 270 ° C. Then, the resistance value R 2 and the fixing strength S 2 after the reflow heat treatment were measured, and the resistance change rate ΔR 2 after the reflow was calculated based on the formula (2).
ΔR=(R−R)/R×100…(2)
表1は試料番号1〜6の導電性接合材料の仕様と実験結果を示している。
ΔR 2 = (R 2 −R 0 ) / R 0 × 100 (2)
Table 1 shows the specifications and experimental results of the conductive bonding materials of sample numbers 1 to 6.
評価基準として、接続抵抗の初期値Rが200mΩ以下、抵抗変化率ΔR、ΔR ±が200%以下、及び各固着強度が10N/mm以上の全てを満足する試料を良品と判定し、これらの評価基準のうち、いずれか一つでも満足しなかった試料を不良品とした。さらに、良品のうち、接続抵抗の初期値Rが100mΩ以下、抵抗変化率ΔR、ΔR が±100%以下、各固着強度が20N/mm以上の全てを満足する試料を優秀品とした。表1中、判定の欄には、優秀品を◎印、良品を〇印、不良品を×印で示している。As evaluation criteria, a sample satisfying all of the initial values R 0 of the connection resistance of 200 mΩ or less, the resistance change rates ΔR 1 and ΔR 2 ± of 200% or less, and the respective fixing strengths of 10 N / mm 2 or more is judged as a non-defective product. A sample that did not satisfy any one of these evaluation criteria was regarded as a defective product. Furthermore, among non-defective products, samples satisfying all of the initial values R 0 of the connection resistance of 100 mΩ or less, the resistance change rates ΔR 1 and ΔR 2 of ± 100% or less, and the respective fixing strengths of 20 N / mm 2 or more are regarded as excellent products. did. In Table 1, in the judgment column, excellent products are indicated by ◎, non-defective products are indicated by ○, and defective products are indicated by ×.
この表1から明らかなように、試料番号1は金属粉末(Sn−58Bi粉末及びCu粉末)の総含有量が70重量%と75重量%を下回っているため、接続抵抗の初期値Rが470mΩとなって200mΩを超え、またPCT後の抵抗変化率ΔRも390%となって200%を超え、さらにPCT後の固着強度も14N/mmとなって20N/mm以下に低下した。これは導電性接合材料中の金属粉末の含有量が少ないため、加熱硬化時にSn−58Bi粉末の濡れ拡がりが不足し、このため十分な導電パスの生成がなされず、融点が300℃以上の高融点反応物を十分に得ることができないため、PCT後の導通性や固着強度が低下し、耐湿性劣化を招いたものと思われる。As apparent from Table 1, sample No. 1 has a total content of metal powders (Sn-58Bi powder and Cu powder) of less than 70 wt% and 75 wt%, so that the initial value R 0 of the connection resistance is exceed 200mΩ become 470Emuomega, also exceed 200% is the rate of change in resistance [Delta] R 1 also 390 percent after the PCT, dropped to 20 N / mm 2 or less further a fixing strength 14N / mm 2 after PCT . This is because the content of the metal powder in the conductive bonding material is small, so that wetting and spreading of the Sn-58Bi powder is insufficient at the time of heat curing, so that a sufficient conductive path is not generated, and the melting point is high at 300 ° C. or higher. Since the melting point reactant cannot be obtained sufficiently, the conductivity and fixing strength after PCT are lowered, and it seems that the moisture resistance is deteriorated.
また、試料番号6は、金属粉末(Sn−58Bi粉末及びCu粉末)の総含有量が93重量%と88重量%を超えているため、固着強度が初期値Sでも7N/mmと低く、PCT後やリフロー処理後はそれぞれ4N/mm、2N/mmと更に低くなった。これは接合界面における機械的な接着性を確保するための樹脂成分が相対的に少ないため、固着強度の低下を招いたものと思われる。In sample No. 6, the total content of the metal powder (Sn-58Bi powder and Cu powder) exceeds 93% by weight and 88% by weight, so the fixing strength is as low as 7 N / mm 2 even at the initial value S 0. After PCT and after reflow treatment, the values were further reduced to 4 N / mm 2 and 2 N / mm 2 , respectively. This is presumably because the resin component for securing the mechanical adhesiveness at the joint interface is relatively small, resulting in a decrease in the fixing strength.
これに対し試料番号2〜5は、金属粉末の総含有量が75〜88重量%であり、しかも、Sn−58Bi粉末の平均粒径D1とCu粉末の平均粒径D2との粒径比D1/D2が2.0と本発明範囲内であり、Sn−58Bi粉末の金属粉末の総量に対する体積比率が50体積%と好ましい範囲であるので、接続抵抗の初期値Rが21〜130mΩ、PCT後の抵抗変化率ΔRが2〜16%、リフロー後の抵抗変化率ΔR が5〜−25%、固着強度が初期値で15〜31N/mm、PCT後で10〜25N/mm、リフロー後で16〜22N/mmといずれも良好な結果を得た。特に、金属粉末の総含有量が83〜86重量%の試料番号3、4は、接続抵抗の初期値Rが21〜58mΩ、PCT後の抵抗変化率ΔRが3〜8%、リフロー後の抵抗変化率ΔR が5〜−25%、固着強度が初期値で29〜31N/mm、PCT後で21〜25N/mm、リフロー後で20N/mmと極めて良好な結果が得られた。In contrast, Sample Nos. 2 to 5 have a total metal powder content of 75 to 88% by weight, and a particle size ratio D1 between the average particle size D1 of the Sn-58Bi powder and the average particle size D2 of the Cu powder. / D2 is 2.0, which is within the range of the present invention, and the volume ratio of Sn-58Bi powder to the total amount of metal powder is 50% by volume, so the initial value R 0 of connection resistance is 21 to 130 mΩ, PCT the rate of change in resistance [Delta] R 1 2 to 16 percent after the resistance change rate [Delta] R 2 is 5-25 percent after reflow, 15~31N / mm 2 fixation strength at the initial value, PCT later 10~25N / mm 2 After reflow, good results were obtained at 16-22 N / mm 2 . In particular, sample numbers 3 and 4 having a total content of metal powder of 83 to 86% by weight have an initial connection resistance value R 0 of 21 to 58 mΩ, a resistance change rate ΔR 1 after PCT of 3 to 8%, and after reflow. the resulting rate of change in resistance [Delta] R 2 is 5-25 percent, 29~31N / mm 2 fixation strength at the initial value, PCT later 21~25N / mm 2, very good results and 20 N / mm 2 after reflow It was.
尚、試料番号2の試料を、樹脂に埋め込んだ後、研磨し、ランド電極と外部電極との界面の断面を観察しところ、導電性接合材料中に分散させたSn−58Bi粉末は、外部電極を形成するSnやランド電極を形成するAg−Pd、さらにはCu粉末との間で高融点反応物を形成しており、これにより良好な接続信頼性の得られていることが確認された。   The sample No. 2 was embedded in resin and then polished, and the cross section of the interface between the land electrode and the external electrode was observed. The Sn-58Bi powder dispersed in the conductive bonding material was A high melting point reaction product was formed between Sn forming Ni, Ag-Pd forming a land electrode, and Cu powder, and it was confirmed that good connection reliability was obtained.
高融点金属粉末として、実施例1のCu粉末に代えて、膜厚0.05μmのSnで被覆されたCu粉末(比重:8.86)(以下、「SnコートCu粉末」という。)を使用した以外は、〔実施例1〕と同様の方法で試料番号11〜16の導電性接合材料を作製した。   As the refractory metal powder, a Cu powder coated with Sn having a thickness of 0.05 μm (specific gravity: 8.86) (hereinafter referred to as “Sn coated Cu powder”) is used instead of the Cu powder of Example 1. Except that, conductive bonding materials of sample numbers 11 to 16 were produced in the same manner as in [Example 1].
そして、〔実施例1〕と同様の方法・手順で接続抵抗の初期値R及び固着強度の初期値Sを測定し、さらにPCT後及びリフロー処理後の各抵抗変化率ΔR、ΔR、及び固着強度S、Sを算出した。Then, the initial value R 0 of the connection resistance and the initial value S 0 of the fixing strength are measured by the same method and procedure as in Example 1, and each resistance change rate ΔR 1 , ΔR 2 after the PCT and after the reflow process is measured. , And bond strengths S 1 and S 2 were calculated.
表2は試料番号11〜16の導電性接合材料の仕様と実験結果を示している。   Table 2 shows the specifications and experimental results of the conductive bonding materials of sample numbers 11 to 16.
この表2から明らかなように、試料番号11〜16は、試料番号1〜6と略同様の傾向が得られた。   As apparent from Table 2, Sample Nos. 11 to 16 had the same tendency as Sample Nos. 1 to 6.
すなわち、試料番号11は、金属粉末(Sn−58Bi粉末及びSnコートCu粉末)の総含有量が70重量%と75重量%を下回っているため、試料番号1と略同様の理由から、接続抵抗の初期値Rが330mΩとなって200mΩを超え、またPCT後の抵抗変化率ΔRが260%となって200%を超え、さらにPCT後の固着強度も15N/mmとなって20N/mm以下に低下した。That is, since the total content of the metal powder (Sn-58Bi powder and Sn-coated Cu powder) is less than 70% by weight and 75% by weight, the sample number 11 has connection resistance for the same reason as the sample number 1. Initial value R 0 of 330 mΩ exceeds 200 mΩ, and resistance change rate ΔR 1 after PCT exceeds 260% and exceeds 200%. Further, the fixing strength after PCT becomes 15 N / mm 2 and becomes 20 N / It decreased to mm 2 or less.
また、試料番号16は、金属粉末の総含有量が93重量%と88重量%を超えているため、試料番号6と略同様の理由から、固着強度が初期値Sでも16N/mmと低く、PCT後やリフロー処理後はそれぞれ3N/mm、8N/mmと更に低くなった。Sample No. 16 has a total content of metal powder exceeding 93% by weight and 88% by weight. Therefore, for substantially the same reason as Sample No. 6, the fixing strength is 16 N / mm 2 even at the initial value S 0. low, after PCT and after reflow treatment was further reduced with each 3N / mm 2, 8N / mm 2.
これに対し試料番号12〜15は、金属粉末の含有量が75〜88重量%であり、しかも、Sn−58Bi粉末の平均粒径D1とSnコートCu粉末の平均粒径D2との粒径比D1/D2が2.0と本発明範囲内であり、Sn−58Bi粉末の全金属粉末に対する体積比率が50体積%と好ましい範囲であるので、接続抵抗の初期値Rが33〜102mΩ、PCT後の抵抗変化率ΔRが2〜14%、リフロー後の抵抗変化率ΔR が4〜−18%、固着強度は初期値で17〜33N/mm、PCT後で14〜28N/mm、リフロー後で15〜21N/mmといずれも良好な結果を得た。特に、金属粉末の総含有量が83〜86重量%の試料番号13、14は、接続抵抗の初期値Rが33〜36mΩ、PCT後の抵抗変化率ΔRが2〜4%、リフロー後の抵抗変化率ΔR が4〜−18%、固着強度が初期値で30〜31N/mm、PCT後で21〜28N/mm、リフロー後で20〜21N/mmと極めて良好な結果を得た。On the other hand, Sample Nos. 12 to 15 have a metal powder content of 75 to 88% by weight, and the particle size ratio between the average particle size D1 of the Sn-58Bi powder and the average particle size D2 of the Sn-coated Cu powder. Since D1 / D2 is 2.0, which is within the range of the present invention, and the volume ratio of Sn-58Bi powder to the total metal powder is 50% by volume, the initial value R 0 of the connection resistance is 33 to 102 mΩ, PCT the rate of change in resistance [Delta] R 1 2 to 14 percent after the resistance change rate [Delta] R 2 is 4-18 percent after reflow, bonding strength is 17~33N / mm 2 in initial value, PCT later 14~28N / mm 2 After reflowing, good results were obtained at 15 to 21 N / mm 2 . In particular, Sample Nos. 13 and 14 having a total content of metal powder of 83 to 86% by weight have an initial connection resistance value R 0 of 33 to 36 mΩ, a resistance change rate ΔR 1 after PCT of 2 to 4%, and after reflow. rate of change in resistance [Delta] R 2 is 4-18 percent, 30~31N / mm 2 fixation strength at the initial value, PCT later 21~28N / mm 2, very good results 20~21N / mm 2 after reflow Got.
尚、〔実施例1〕との比較では、総体的に接続抵抗及び固着強度の双方で向上することが分かった。これはCu粉末がSn−58Bi粉末に対して濡れ性の高いSnで被覆されているため、導電パスの形成や、高融点反応物の生成が促進されたものと思われる。   In comparison with [Example 1], it was found that both the connection resistance and the fixing strength were improved overall. This is probably because the Cu powder was coated with Sn having high wettability with respect to the Sn-58Bi powder, so that formation of a conductive path and generation of a high melting point reactant were promoted.
低融点金属粉末としてSn−58Bi粉末(比重:8.93)を使用し、高融点金属粉末としてSnコートCu粉末(比重:8.86)を使用し、〔実施例1〕と同様の方法により、粒径比D1/D2が0.2〜10.0の範囲で異なる試料番号21〜25の導電性接合材料を作製した。   Sn-58Bi powder (specific gravity: 8.93) was used as the low melting point metal powder, Sn coated Cu powder (specific gravity: 8.86) was used as the high melting point metal powder, and the same method as in Example 1 was used. The conductive bonding materials of sample numbers 21 to 25 having different particle size ratios D1 / D2 in the range of 0.2 to 10.0 were prepared.
そして、〔実施例1〕と同様の方法・手順で接続抵抗の初期値R及び固着強度の初期値Sを測定し、さらにPCT後及びリフロー処理後の各抵抗変化率ΔR、ΔR、及び固着強度S、Sを算出した。Then, the initial value R 0 of the connection resistance and the initial value S 0 of the fixing strength are measured by the same method and procedure as in Example 1, and each resistance change rate ΔR 1 , ΔR 2 after the PCT and after the reflow process is measured. , And bond strengths S 1 and S 2 were calculated.
表3は試料番号21〜25の導電性接合材料の仕様と実験結果を示している。   Table 3 shows the specifications and experimental results of the conductive bonding materials of sample numbers 21 to 25.
この表3から明らかなように、試料番号21は、粒径比D1/D2が0.2であり、0.5未満であるため、PCT後の抵抗変化率ΔRが210%となって200%を超えている。これはSnコートCu粉末同士の間隔に対しSn−58Bi粉末の平均粒径D1が小さすぎるため、加熱硬化時にSn−58Bi粉末が濡れ拡がってもSnコートCu粉末同士をSn−58Bi粉末で巧く接続することができない箇所が生じ、このため導電性の良好な導電パスを十分に形成することができず、その結果高温多湿下で長時間晒されると接続抵抗が上昇し、導通性が低下するものと考えられる。 As is clear from Table 3, Sample No. 21 is a particle size ratio D1 / D2 is 0.2, because it is less than 0.5, the rate of change in resistance [Delta] R 1 after PCT is a 210% 200 % Is over. This is because the average particle diameter D1 of the Sn-58Bi powder is too small with respect to the interval between the Sn-coated Cu powders, so that even if the Sn-58Bi powders are wet and spread during heat curing, the Sn-coated Cu powders are skillfully made with Sn-58Bi powders. A part that cannot be connected is generated, so that a conductive path with good conductivity cannot be formed sufficiently. As a result, when exposed to a long time under high temperature and high humidity, the connection resistance increases and the conductivity decreases. It is considered a thing.
また、試料番号25は、粒径比D1/D2が10.0と6.0を超えているため、リフロー後の抵抗変化率ΔRが1070%となって200%を大幅に超えることが分かった。また、固着強度が初期値Sでも19N/mmと低く、PCT後やリフロー処理後はそれぞれ18N/mm、9N/mmと更に低くなった。これはSnコートCu粉末の平均粒径D2に対するSn−58Bi粉末の平均粒径D1が大きすぎるため、加熱硬化時にSn−58Bi粉末同士が融着し、又はSn−58Bi粉末がランド電極や外部電極に濡れ拡がり、SnコートCu粉末間をつなぐ導電パスの形成が不足し、このため、SnコートCu粉末とランド電極及び外部電極との接合強度を十分に得ることができず、固着力が劣化し、さらには耐熱性も劣化したものと思われる。Further, Sample No. 25, since the particle size ratio D1 / D2 is greater than 10.0 and 6.0, found that resistance change rate [Delta] R 2 after reflow is greatly exceed 200% becomes 1070% It was. Further, the bonding strength is the initial value S 0 even 19N / mm 2 and low after PCT and after reflow treatment was further lowered respectively 18N / mm 2, 9N / mm 2. This is because the average particle diameter D1 of the Sn-58Bi powder is too large with respect to the average particle diameter D2 of the Sn-coated Cu powder, so that the Sn-58Bi powder is fused with each other at the time of heat curing, or the Sn-58Bi powder is a land electrode or an external electrode. As a result, the conductive path connecting between the Sn-coated Cu powder and the Sn-coated Cu powder is insufficient, so that sufficient bonding strength between the Sn-coated Cu powder and the land electrode and the external electrode cannot be obtained, resulting in deterioration of the adhesion force. Furthermore, it seems that heat resistance has also deteriorated.
これに対し試料番号21〜24は、粒径比D1/D2が0.5〜6.0であり、しかも金属粉末(Sn−58Bi粉末及びSnコートCu粉末)の総含有量が86重量%と本発明範囲内であり、Sn−58Bi粉末の金属粉末の総量に対する体積比率が50体積%と好ましい範囲であるので、接続抵抗の初期値Rが36〜71mΩ、PCT後の抵抗変化率ΔRが4〜18%、リフロー後の抵抗変化率ΔR が−5〜−22%、固着強度が初期値で30〜39N/mm、PCT後で17〜25N/mm、リフロー後で21〜35N/mmといずれも良好な結果を得た。特に、粒径比D1/D2が0.5〜2.0の試料番号22、23は、接続抵抗の初期値Rが36〜48mΩ、PCT後の抵抗変化率ΔRが4〜18%、リフロー後の抵抗変化率ΔR が−5〜−18%、固着強度が初期値で30〜39N/mm、PCT後で23〜25N/mm、リフロー後で21〜33N/mmと極めて良好な結果が得られた。In contrast, Sample Nos. 21 to 24 have a particle size ratio D1 / D2 of 0.5 to 6.0, and the total content of metal powders (Sn-58Bi powder and Sn-coated Cu powder) is 86% by weight. Within the scope of the present invention, the volume ratio of the Sn-58Bi powder to the total amount of the metal powder is a preferable range of 50% by volume. Therefore, the initial value R 0 of the connection resistance is 36 to 71 mΩ, and the resistance change rate ΔR 1 after PCT but 4-18%, rate of change in resistance [Delta] R 2 is -5 22% after reflow, 30~39N fixing strength at the initial value / mm 2, PCT later 17~25N / mm 2, 21~ after reflow A good result was obtained at 35 N / mm 2 . In particular, Sample No. 22 and 23 of the particle size ratio D1 / D2 is 0.5 to 2.0, the initial value R 0 of connection resistance 36~48Emuomega, the rate of change in resistance [Delta] R 1 after PCT is 4 to 18%, rate of change in resistance [Delta] R 2 is -5 18% after reflow, 30~39N fixing strength at the initial value / mm 2, PCT later 23~25N / mm 2, very and 21~33N / mm 2 after reflow Good results were obtained.
Sn−58Bi粉末とSnコートCu粉末を用意し、〔実施例1〕と同様の方法により、金属粉末(Sn−58Bi粉末及びSnコートCu粉末)の総量に対するSn−58Bi粉末の体積比率が、20〜80体積%の範囲で異なる試料番号31〜36の導電性接合材料を〔実施例1〕と同様の方法で作製した。   Sn-58Bi powder and Sn-coated Cu powder were prepared, and the volume ratio of Sn-58Bi powder to the total amount of metal powder (Sn-58Bi powder and Sn-coated Cu powder) was 20 by the same method as in [Example 1]. Conductive bonding materials having different sample numbers 31 to 36 in a range of ˜80% by volume were produced in the same manner as in [Example 1].
次いで、〔実施例1〕と同様の方法・手順で接続抵抗の初期値R及び固着強度の初期値Sを測定し、さらにPCT後及びリフロー処理後の各抵抗変化率ΔR、ΔR、及び固着強度S、Sを算出した。Next, the initial value R 0 of the connection resistance and the initial value S 0 of the fixing strength are measured by the same method and procedure as in Example 1, and each resistance change rate ΔR 1 , ΔR 2 after the PCT and after the reflow treatment is measured. , And bond strengths S 1 and S 2 were calculated.
表4は試料番号31〜36の導電性接合材料の仕様と実験結果を示している。   Table 4 shows the specifications and experimental results of the conductive bonding materials of sample numbers 31 to 36.
この表4から明らかなように、接続抵抗の初期値Rが46〜200mΩ、PCT後の抵抗変化率ΔRが4〜180%、リフロー後の抵抗変化率ΔR が−65〜150%、固着強度が初期値で21〜36N/mm、PCT後で10〜28N/mm、リフロー後で10〜42N/mmといずれも良好な結果が得られた。As is apparent from Table 4, the initial value R 0 of the connection resistance is 46 to 200 mΩ, the resistance change rate ΔR 1 after PCT is 4 to 180%, the resistance change rate ΔR 2 after reflow is −65 to 150%, 21~36N fixation strength at the initial value / mm 2, PCT later 10~28N / mm 2, 10~42N / mm 2 both with good results were obtained after reflow.
しかしながら、試料番号31は、金属粉末の総量に対するSn−58Bi粉末の体積比率が20体積%であり、25体積%以下と低いため、Sn−58Bi粉末の占める体積比率が少なくなって導電パスの形成が妨げられ、このため接続抵抗の初期値Rが110mΩ、PCT後の抵抗変化率ΔRが110%となり、またPCT後の固着強度が10N/mmとなり、試料番号32〜35に比べて実用上問題の無いレベルであるが、電気的及び機械的強度が比較的劣ることが分かった。However, in Sample No. 31, the volume ratio of the Sn-58Bi powder to the total amount of the metal powder is 20% by volume and is as low as 25% by volume or less. Therefore, the initial value R 0 of the connection resistance is 110 mΩ, the resistance change rate ΔR 1 after PCT is 110%, and the fixing strength after PCT is 10 N / mm 2 , which is compared with the sample numbers 32-35. Although it is at a level where there is no problem in practical use, it has been found that the electrical and mechanical strength is relatively inferior.
また、試料番号36は、金属粉末の総量に対するSn−58Bi粉末の体積比率が80体積%であり、75体積%を超えているため、SnコートCu粉末と反応しないSn−58Bi粉末が未反応状態のまま残留し、このため接続抵抗の初期値Rが200mΩ、PCT後の抵抗変化率ΔRが180%、リフロー後の抵抗変化率ΔR が150%、固着強度がPCT後で17N/mm、リフロー後で10N/mmとなり、この場合も試料番号32〜35に比べて実用上問題の無いレベルであるが、導通性の低下を招いたり、高温での接続信頼性が低下し、電気的及び機械的強度が比較的劣ることが分かった。Moreover, since the volume ratio of the Sn-58Bi powder with respect to the total amount of metal powder is 80 volume% and exceeds 75 volume%, the sample number 36 has Sn-58Bi powder which does not react with Sn coat Cu powder in an unreacted state. Therefore, the initial value R 0 of the connection resistance is 200 mΩ, the resistance change rate ΔR 1 after PCT is 180%, the resistance change rate ΔR 2 after reflow is 150%, and the fixing strength is 17 N / mm after PCT. 2 and 10 N / mm 2 after reflow, and in this case as well, it is a level that is practically no problem as compared with sample numbers 32 to 35, but it leads to a decrease in conductivity, and connection reliability at high temperatures decreases, It has been found that the electrical and mechanical strength is relatively poor.
以上より、金属粉末の総量に対するSn−58Bi粉末の体積比率は、25〜75体積%が好ましい範囲であることが確認された。   From the above, it was confirmed that the volume ratio of the Sn-58Bi powder to the total amount of the metal powder is in a preferable range of 25 to 75% by volume.
平均粒径D1が10μmのSn−58Bi粉末と、平均粒径D2が5μmのCu粉末に膜厚0.02μmのAuが被覆されたAuコートCu粉末を使用した以外は、〔実施例1〕と同様の方法・手順で試料番号41の導電性接合材料を作製した。   Example 1 except that Sn-58Bi powder having an average particle diameter D1 of 10 μm and Au-coated Cu powder obtained by coating Au having a film thickness of 0.02 μm on Cu powder having an average particle diameter D2 of 5 μm were used. A conductive bonding material of Sample No. 41 was produced by the same method and procedure.
また、上記AuコートCu粉末に代えて、平均粒径D2が5μmのCu粉末に膜厚0.01μmのInが被覆されたInコートCu粉末を使用した以外は、試料番号41と同様の方法・手順で試料番号42の導電性接合材料を作製した。   Further, in place of the Au-coated Cu powder, the same method as Sample No. 41 was used, except that an In-coated Cu powder in which an In particle having a thickness of 0.01 μm was coated on a Cu powder having an average particle diameter D2 of 5 μm was used. A conductive bonding material of sample number 42 was produced by the procedure.
さらに、導電性接合材料の調製過程で還元性物質を添加しなかった以外は試料番号42と同様の方法・手順で試料番号43の導電性接合材料を作製した。   Furthermore, the conductive bonding material of sample number 43 was produced by the same method and procedure as sample number 42, except that the reducing substance was not added in the process of preparing the conductive bonding material.
次いで、〔実施例1〕と同様の方法・手順で接続抵抗の初期値R及び初期固着強度Sを測定し、さらにPCT後及びリフロー処理後の各抵抗変化率ΔR、ΔR、及び固着強度S、Sを算出した。Next, the initial value R 0 and the initial fixing strength S 0 of the connection resistance are measured by the same method and procedure as in [Example 1], and each resistance change rate ΔR 1 , ΔR 2 after PCT and after reflow treatment, and The fixing strengths S 1 and S 2 were calculated.
表5は試料番号41〜43の導電性接合材料の仕様と実験結果を示している。   Table 5 shows the specifications and experimental results of the conductive bonding materials of sample numbers 41 to 43.
この表5から明らかなように、試料番号43は、接続抵抗の初期値Rは7300mΩとなって導通性が低下し、またPCT後の抵抗変化率ΔR1も790%と高くなり、PCT後の固着強度も9N/mmに低下した。これは導電性接合材料中に還元剤が含有されていないため、InコートCu粉末の表面には酸化物が除去されずに残存し、このため熱硬化性樹脂の加熱硬化時にはSn−58Bi粉末がInコートCu粉末の表面に濡れ拡がりにくく、高融点反応物の生成が促進されなくなるためと思われる。As is apparent from Table 5, the sample No. 43 has an initial value R 0 of the connection resistance of 7300 mΩ, the conductivity decreases, and the resistance change rate ΔR1 after PCT also increases to 790%. The fixing strength also decreased to 9 N / mm 2 . This is because the conductive bonding material does not contain a reducing agent, so that the oxide remains on the surface of the In-coated Cu powder, so that the Sn-58Bi powder is not heated during the thermosetting of the thermosetting resin. This is probably because the surface of the In-coated Cu powder hardly spreads on the surface and the generation of the high melting point reactant is not promoted.
これに対し試料番号41及び42は導電性接合材料中に還元性物質としてのこはく酸が含有されており、しかも金属粉末の総含有量が86重量%、粒径比D1/D2が2.0といずれも本発明範囲内であり、さらにSn−58Bi粉末の金属粉末の総量に対する体積比率が50体積%と好ましい範囲であるので、接続抵抗の初期値Rが21〜28mΩ、PCT後の抵抗変化率ΔRが4〜6%、リフロー後の抵抗変化率ΔR が35〜−10%、固着強度が初期値で28〜33N/mm、PCT後で20〜25N/mm、リフロー後で27〜30N/mmといずれも極めて良好な結果が得られることが分かった。On the other hand, Sample Nos. 41 and 42 contain succinic acid as a reducing substance in the conductive bonding material, and the total content of the metal powder is 86% by weight, and the particle size ratio D1 / D2 is 2.0. Are within the scope of the present invention, and the volume ratio of the Sn-58Bi powder to the total amount of the metal powder is a preferable range of 50% by volume. Therefore, the initial value R0 of the connection resistance is 21 to 28 mΩ, the resistance after PCT. rate of change [Delta] R 1 is 4% to 6%, the rate of change in resistance [Delta] R 2 is 35 to-10 percent after reflow, 28~33N / mm 2 fixation strength at the initial value, PCT later 20~25N / mm 2, after reflow It was found that very good results were obtained at 27 to 30 N / mm 2 .

Claims (7)

  1. 熱硬化性樹脂と、該熱硬化性樹脂の熱硬化温度以下の温度で溶融するSn−Bi合金粉末からなる第1の金属粉末と、前記熱硬化性樹脂の熱硬化温度以下の温度で溶融せず、かつ前記熱硬化性樹脂の加熱硬化時に前記第1の金属粉末と反応して300℃以上の高融点を有する反応物を生成する第2の金属粉末と、該第2の金属粉末の表面に形成される酸化物を除去する還元性物質とを含有し、
    前記第1の金属粉末及び前記第2の金属粉末の含有量が、総計で75〜88重量%であり、
    かつ、前記第1の金属粉末の平均粒径D1と前記第2の金属粉末の平均粒径D2との粒径比D1/D2が、0.5〜6.0であることを特徴とする導電性接合材料。
    A first metal powder composed of a thermosetting resin, a Sn-Bi alloy powder that melts at a temperature lower than the thermosetting temperature of the thermosetting resin, and a temperature lower than the thermosetting temperature of the thermosetting resin; And a second metal powder that reacts with the first metal powder during the heat curing of the thermosetting resin to produce a reactant having a high melting point of 300 ° C. or higher, and a surface of the second metal powder. Containing a reducing substance that removes oxides formed in
    The total content of the first metal powder and the second metal powder is 75 to 88% by weight,
    The particle size ratio D1 / D2 between the average particle diameter D1 of the first metal powder and the average particle diameter D2 of the second metal powder is 0.5 to 6.0. Bonding material.
  2. 前記第1の金属粉末及び前記第2の金属粉末の総量に対する前記第1の金属粉末の体積比率は、25〜75体積%であることを特徴とする請求項1記載の導電性接合材料。  2. The conductive bonding material according to claim 1, wherein a volume ratio of the first metal powder to a total amount of the first metal powder and the second metal powder is 25 to 75% by volume.
  3. 前記第2の金属粉末は、前記第2の金属粉末よりも前記第1の金属粉末に対して濡れ性が高く、かつ、前記熱硬化性樹脂の熱硬化温度以下の温度で溶融する低融点金属で被覆されていることを特徴とする請求項1又は請求項2記載の導電性接合材料。  The second metal powder has a higher wettability with respect to the first metal powder than the second metal powder and melts at a temperature lower than the thermosetting temperature of the thermosetting resin. The conductive bonding material according to claim 1, wherein the conductive bonding material is coated with a conductive material.
  4. 前記第2の金属粉末はCuを主成分とした金属粉末であり、前記低融点金属はSnを含有した金属であることを特徴とする請求項3記載の導電性接合材料。  4. The conductive bonding material according to claim 3, wherein the second metal powder is a metal powder containing Cu as a main component, and the low melting point metal is a metal containing Sn.
  5. 前記第2の金属粉末は、該第2の金属粉末よりも前記第1の金属粉末に対して濡れ性の高い金属で被覆されていることを特徴とする請求項1又は請求項2記載の導電性接合材料。  The conductive material according to claim 1, wherein the second metal powder is coated with a metal having higher wettability with respect to the first metal powder than the second metal powder. Bonding material.
  6. 前記第2の金属粉末はCuを主成分とした金属粉末であり、前記濡れ性が高い金属は貴金属であることを特徴とする請求項5記載の導電性接合材料。  6. The conductive bonding material according to claim 5, wherein the second metal powder is a metal powder containing Cu as a main component, and the metal having high wettability is a noble metal.
  7. 第1の電極を有する第1の電気構造物と、第2の電極を有する第2の電気構造物とを備えた電子装置であって、An electronic device comprising a first electrical structure having a first electrode and a second electrical structure having a second electrode,
    前記第1の電極と前記第2の電極とが、請求項1乃至請求項6のいずれかに記載の導電性接合材料を介して電気的に接続されると共に、  The first electrode and the second electrode are electrically connected via the conductive bonding material according to any one of claims 1 to 6,
    前記第1の金属粉末と前記第2の金属粉末との界面、前記第1の金属粉末と前記第1の電極との界面、及び前記第1の金属粉末と前記第2の電極との界面のうちの少なくとも1つの界面は、300℃以上の高融点を有する反応物で結合されていることを特徴とする電子装置。  The interface between the first metal powder and the second metal powder, the interface between the first metal powder and the first electrode, and the interface between the first metal powder and the second electrode. At least one of the interfaces is bonded with a reactant having a high melting point of 300 ° C. or higher.
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